Divinyl paint composition and painting process

ABSTRACT

A SUBSTRATE IS COATED WITH A FILM-FORMING COMPOSITION COMPRISING A UNIQUE DIVINYL COMPOUND AND THE COATING IS CONVERTED TO A TENACIOUSLY ADHERING, SOLVENT-RESISTANT, WEAR AND WEATHER-RESISTANT, PREFERABLY IN THE FORM OF AN ELECTRON BEAM. THIS DIVINYL COMPOUND IS FORMED BY FIRST REACTING A DIEPOXIDE WITH ACRYLIC ACID AND/OR METHACRYLIC ACID AND SUBSEQUENTLY REACTING THE RESULTANT ESTER CONDENSATION PRODUCT WITH A SATURATED ACYL HALIDE.

United States Patent ()ifice 3,586,529 Patented June 22,, 1971 ABSTRACTon THE DISCLOSURE A substrate is coated with a film-forming compositioncomprising a unique divinyl compound and the coating is converted to atenaciously adhering, solvent-resistant, wear and weather-resistant,preferably in the form of an electron beam. This divinyl compound isformed by first reacting a diepoxide with acrylic acid and/ormethacrylic acid and subsequently reacting the resultant estercondensation product with a saturated acyl halide.

This invention relates to the art of coating. It is particularlyconcerned with a process of painting a substrate having externalsurfaces of wood, glass, metal or polymeric solid with a film formercomprising unique tetravinyl compound and crosslinking such film formerinto a wearresistant, weather-resistant, solvent-resistant, tenaciouslyadhering film by exposing the same to ionizing radiation, preferably inthe form of an electron beam, and to the paint used in this process.

In this application, the term paint is meant to include pigment and/orfinely ground filler, the binder without pigment and/or filler or havingvery little of the same, which can be tinted if desired. Thus, the paintbinder which is ultimately crosslinked by ionizing radiation can be allor virtually all that is used to form the film, or it can be a vehiclefor pigment and/or particulate filler material.

The first reaction step in preparing the divinyl compounds used hereinis illustrated by the representative reaction shown in FIG. 1 of theaccompanying drawing. The second reaction step is illustrated by therepresentative reaction shown in FIG. 2.

The diepoxides employed as starting materials for preparing the divinylcompound of this invention may be of the epichlorohydrin-bisphenol type,the epichlorohydrinpolyalcohol type, or those prepared by reactingdiolefins with peracids, e.g., peracetic acid or other means. Diepoxidesand their preparation are discussed in detail in Modern SurfaceCoatings, Paul Nylen and Edward Sunderland, 1965 Science Publishers, adivision of John Wyley & Sons Ltd., London-New York-Sydney, Library ofCongress Catalog Card Number 65-28344, pp. 197-208. Representativediepoxides include, but not by way of limitation, the following:

( 1)3,4-epoxy-6-methyl-cyclohexylmethyl-3,4-epoxymethylcyclohexanecarboxylate.

(2) l-epoxyethyl-3,4 epoxycyclohexene.

(3) dipentene dioxide (limonene dioxide).

(4) dicyclopentadienedioxide.

(5) diepoxides having structural formula in accordance with thefollowing:

Other suitable diepoxides are disclosed in US. Pats. 2,890,202;3,256,226; 3,373,221 and elsewhere throughout the literature. a

The diepoxides employed will usually have molecular weights below about2,000, more commonly in the range of about to about 500. Usually thediepoxides will consist of carbon, hydrogen and oxygen but they may besubstituted, if desired, with non-interfering substituents, such ashalogen atoms, ether radicals and the like. They may be saturated orunsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic. Theymay be monomeric or polymeric.

The acyl halides are preferably a chloride of a C C preferably a C -Csaturated, aliphatic monocarboxylic acid but other may be used, e.g.,the corresponding bromides. The resultant divinyl compounds used hereinare homopolymerizable and copolymerizable with monoand divinyl monomers,e.g., styrene, vinyl tolulene, alpha-methyl styrene, divinyl benzene,methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate,hydroxypropyl methacrylate, glycidyl methacrylate, etc., the divinylreaction product formed by reacting a 'monoepoxide with acrylic acid ormethacrylic acid and then reacting the resultant ester condensationproduct with a vinyl unsaturated acyl halide, the divinyl reactionproduct formed by reacting a diepoxide with two molar parts of acrylicacid or methacrylic acid, the divinyl reaction product formed byreacting a diepoxide with two molar parts of acrylic acid or methacrylicacid and subsequently reacting the resultant ester condensation productwith two molar parts of a saturated acyl halide, e.g., acetyl chlorideor an efiectively saturated acyl halide, e.g., benzoyl chloride, thedivinyl reaction product formed by reacting one molar part of adiepoxide with two molar parts of acrylic or methacrylic acid andsubsequently reacting the resultant ester condensation product with twomolar parts of an alpha-beta olefinically unsaturated acyl halide havingan aromatic radical affixed to the beta carbon of the olefinic linkage,e.g., cinnamic acid chloride, tetravinyl compounds formed by reacting adiepoxide with two molar parts of acrylic or methacrylic acid andsubsequently reacting the resultant ester condensation product with twomolar parts of a vinyl unsaturated acyl halide, an alpha-betaolefinically unsaturated polymer, etc.

The divinyl adducts used herein have lowered viscosities than thecorresponding divinyl compounds produced by the aforementioned firstreaction step, i.e., the product produced by reacting a diepoxide withtwo moles of acrylic or methacrylic acid. They are also more soluble inorganic solvents. In paints, they provide films of greater flexibilitythan those provided by corresponding amounts of the tetravinyl compoundsherein described and illustrated.

A minor portion, i.e., up to slightly below about 50 weight percent ofthe divnyl compound may be replaced With a. different divinyl compoundor a tetravinyl compound consisting essentially of carbon, hydrogen andoxygen and having a molecular weight below about 260 0, preferably about220 to about 1100, more preferably about 220 to about 650, such as oneof the divinyl or tetravinyl compounds herein mentioned and illustrated.

The films formed from the paints of this invention are advantageouslycured at relatively low temperatures, e.g., below room temperature(20-25 C.) and about 70 C. The radiation energy is applied at dose ratesof about 0.1 to about 100 Mrad per second upon a preferably movingworkpiece until the wet film is converted to a tackfree state or untilthe film is exposed to a desired dosage.

The film-forming material advisedly has an application viscosity lowenough to permit rapid application to the substrate in substantiallyeven depth and high enough so that at least a l-mil (0.001 inch) filmwill hold on a vertical surface Without sagging. Such film willordinarily be applied to an average depth of about 0.1 to about 4 milswith the appropriate adjustment in viscosity and application technique.It Will be obvious to those skilled in the art that the choice ofdiepoxide used in preparing the divinyl compound can be varied so as tovary the viscosity of the resultant product. Likewise, the viscosity ofthe total film-forming composition can be varied by the choice of otherpolymerizable components of the coating composition. The viscosity canalso be adjusted by the addition of nonpolymerizable, volatile solvents,e.g., acetone, toluene, xylene, etc., which can be flashed off afterapplication. By one or more such adjustments, the viscosity of the paintbinder solution can be adapted for application by conventional paintapplication techniques, e.g., spraying, roll coating, etc. The paintbinder is preferably applied to the substrate and cured thereon as acontinuous film of substantially even depth.

This invention will be more fully understood from the followingillustrative examples:

EXAMPLE 1 A divinyl compound is prepared in the manner below set forthfrom the material hereinafter named:

(1) To the reaction vessel equipped with condenser, stirrer, nitrogeninlet and thermometer are charged the following materials:

Materials: Parts by weight (a) Diepoxide 192 (b) Methacrylic acid 86|(c) Toluene (solvent) 500 (d) Dimethylbenzylamine (catalyst) 1 1 Seefollowing formula:

i i i i (2) The diepoxide, the methacrylic acid and the dimethylbenzylamine are intimately mixed and incrementally added to the toluenewhich is at 90 C. in a nitrogen atmosphere.

(3) The reaction mixture is maintained at 90 C. until reaction of theepoxide groups is essentially complete as measured by product acidnumber of less than about 10.

'(4) The solvent is removed under vacuum and a solid reaction product(softening point 45 C.) is recovered.

(5) The solid reaction product of '(4) in the amount of 280 parts byWeight is dissolved in 500 parts by weight toluene, and 95 parts byweight of butyric acid chloride are added dropwise with the reactionmixture maintained at 65 C. until HCl evolution ceases.

(6) The solvent is removed under vacuum and a divinyl compound isrecovered.

Substrates of wood, glass, metal and polymeric solid, i.e.,polypropylene and acrylonitrile-butadiene-styrene copolymer are coatedWith this divinyl compound using the following procedure:

(1) The above prepared divinyl compound is diluted to spraying viscositywith xylene and the paint film is sprayed on the aforementionedsubstrates to an average depth to about 1 mil (0.001 inch) and thesolvent flashed off.

(2) The coated substrate is passed through a nitrogen atmosphere and ata distance of about 10 inches below the electron emission window of acathode ray type, electron accelerator through which an electron beam isprojected upon the coated surface until the Wet coating is polymerizedto a tack-free state. The electrons of this beam have an average energyof about 275,000 electron volts with a current of about 25 milliamperes.

EXAMPLE 2 The procedure of Example 1 is repeated except that thediepoxide employed is 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxymethyl cyclohexanecarboxylate and the paintfilm is applied to an average depth of about 3 mils.

EXAMPLE 3 The procedure of Example 1 is repeated except that thediepoxide employed is 1-epoxyethyl-3,4-epoxycyc1ohexane.

EXAMPLE 4 The procedure of Example 1 is repeated except that thediepoxide employed is dipentene dioxide.

EXAMPLE 5 The procedure of Example 1 is repeated except that thediepoxlde employed is dicyclopentadiene dioxide.

EXAMPLE 6 The procedure of Example 1 is repeated except that thediepoxide employed has structural formula in accordance with the formulahereinbefore set forth and identified as diepoxide (5)(a) wherein n is4.

EXAMPLE 7 The procedure of Example 1 is repeated except that thediepoxide employed has structural formula in accordance with the formulahereinbefore set forth and identified as diepoxide (5) (b).

EXAMPLE 8 The procedure of Example 1 is repeated except that thediepoxide employed has structural formula in accordance with the formulahereinbefore set forth and identified as diepoxide (5)(c) wherein n is4.

EXAMPLE 9 The procedure of Example 1 is repeated with the soledifference that the electrons of the electron beam have an averageenergy of about 350,000 electron volts.

EXAMPLE 10 The procedure of Example 1 is repeated With the soledifference that the atmosphere of irradiation is helium.

EXAMPLE 11 The procedure of Example 1 is repeated with the soledifference that acetyl chloride is substituted for the butyric acidchloride.

EXAMPLE 12 The procedure of Example 1 is repeated with the soledifference that butyric acid bromide is substituted for butyric acidchloride.

EXAMPLE 13 The procedure of Example 1 is repeated with the soledifference that hexanoic acid chloride is substituted for the butyricacid chloride.

EXAMPLE 14 The procedure of Example 1 is repeated with the soledifference that capric (decanoic) acid chloride is substituted for thebutyric acid chloride.

EXAMPLE 15 The procedure of Example 1 is repeated with the soledifference that lauric (dodecanoic) acid chloride is sub stituted forthe butyric acid chloride.

EXAMPLE 16 The procedure of Example 1 is repeated with the soledifference that stearic (octodecanoic) acid chloride is substituted forthe butyric acid chloride.

EXAMPLE 17 The procedure of Example 1 is repeated with the soledifference that the diepoxide is first reacted with a mixture of acrylicacid and methacrylic acid.

EXAMPLE 18 A divin'yl compound is prepared as in Example 1 and atetravinyl compound is prepared using the same procedure with the singleexception that methacryloyl chloride is substituted for the second stepreactant butyric acid chloride. Substrates are then coated as in Example1 using a paint binder composition consisting of 51 parts by Weight ofthe divinyl compound, 49 parts by weight of the tetravinyl compound, andacetone in an amount sufficient to provide the composition with goodspraying viscosity. The substrates are coated with this composition andthe acetone flashed off prior to irradiation. Irradiation conditions arethe same as in Example 1.

Additional substrates are coated in like manner except that the paintbinder composition consists of 99 parts by weight of said divinylcompound, 1 part by Weight of said tetravinyl compound and said acetone.

Additional substrates are coated in like manner except that the paintbinder composition consists of 75 parts by weight of said divinylcompound, 25 parts by weight of said tetravinyl compound and saidacetone.

EXAMPLE 19 A divinyl compound is prepared as in Example 1 and adifferent divinyl compound is prepared using the same procedure with thesingle exception that cinnamic acid chloride is substituted for thesecond step reactant butyric acid chloride. Substrates are then coatedas in Example 1 using a paint binder composition consisting of 51 partsby weight of the divinyl compound prepared with butyric acid chloride,49 parts by weight of the divinyl compound prepared with cinnamic acidchloride, and toluene in an amount sufiicient to provide the compositionwith a good spraying viscosity. Substrates are coated with thiscomposition and toluene flashed off prior to irradiation. Irradiationconditions are the same as in Example 1.

Additional substrates are coated in like manner except that the paintbinder composition consists of 99 parts by weight of the divinylcompound prepared with butyric acid chloride, one part by weight of thedivinyl compound prepared with cinnamic acid chloride and said toluene.

Additional substrates are coated in like manner except that the paintbinder composition consists of 75 parts by weight of the divinylcompound prepared with butyric acid chloride, 25 parts by weight of thedivinyl compound, prepared with cinnamic acid chloride and said toluene.

EXAMPLE 20 A divinyl compound is prepared as in Example 1 and adifferent divinyl compound is prepared using the same procedure with thesingle exception that one molar part of cyclopentene oxide is used inlieu of the diepoxide and is reacted with one molar part of methacrylicacid to open the epoxide ring. The resultant monovinyl compound is thenreacted with methacryloyl chloride to prowide a divinyl compound.Substrates are coated as in Example 1 using a paint binder compositionconsisting of 51 parts by weight of the divinyl compound prepared withthe diepoxide, 49 parts by weight of the divinyl compound derived fromthe monoepoxide, and xylene in amounts sufficient to provide thecomposition of good spraying consistency. The substrates are coated Withthis composition and the xylene flashed off prior to the irradiation.The irradiation conditions are the same as in Example 1.

Additional substrates are coated in like manner except that the paintbinder composition consists of 99 parts by Weight of the divinylcompound prepared from the diepoxide, one part by Weight of the divinylcompound derived from the monoepoxide and said xylene.

Additional substrates are coated in like manner except that the paintbinder composition consists of 75 parts by weight of the divinylcompound prepared from the diepoxide, 25 parts by weight of the divinylcompound derived from the monoepoxide, and said Xylene.

EXAMPLE 21 A divinyl compound is prepared as in Example 1 and adifferent divinyl compound is prepared using only the procedure employedin the first step procedure used in preparing the divinyl compound ofExample 1, i.e., the diepoxide is reacted with two molar parts ofmethacrylic acid and the resultant dihydroxy divinyl compound isrecovered and used. Substrates are coated as in Example 1 using a paintbinder composition consisting of 51 parts by weight of the divinylcompound whose preparation includes the use of butyric acid chloride, 49parts by weight of the divinyl compound formed solely by reacting thediepoxide with two molar parts of methacrylic acid, and xylene inamounts sufficient to provide the composition of good sprayingconsistency. Substrates are coated with this composition and the xyleneflashed off prior to irradiation. The irradiation conditions are thesame as in Example 1.

Additional substrates are coated in like manner except that the paintbinder composition consists of 99 parts by weight of the divinylcompound whose preparation includes the use of butyric acid chloride,one part by weight of the divinyl compound formed solely by reacting thediepoxide with two molar parts of methacrylic acid, and said saidxylene.

Additional substrates are coated in like manner except that the paintbinder composition consists of 75 parts by weight of the divinylcompound whose preparation includes the use of butyric acid chlorides,25 parts by Weight of the divinyl compound formed solely by reacting thediepoxide with two molar parts of methacrylic acid, and said xylene.

EXAMPLE 22 The procedure of Example 19 is repeated except for the soledifference that benzoyl chloride is substituted for the cinnamic acidchloride.

The term ionizing radiation as employed herein means radiation havingsufiicient energy to effect polymerization of the paint films hereindisclosed, i.e., energy equivalent to that of about 5,000 electron voltsor greater. A preferred method of curing films of the instant paint onsubstrates to which they have been applied is by subjecting such filmsto a beam of polymerization effecting electrons having an average energyin the range of about 100,000 to about 500,000 electron volts. Whenusing such a beam, it is preferred to employ a minimum of about 25,000electron volts per inch for distance between the radiation emitter andthe workpiece when the intervening space is occupied by air. Adjustmentscan be made for the relative resistance of the intervening gas which ispreferably an oxygen-free inert gas such as hydrogen or helium.

The abbreviation rad as employed herein means that dose of radiationwhich results in the absorption of 100 ergs of energy per gram ofabsorber, e.g., coating film. The abbreviation Mrad as employed hereinmeans 1 million rad. The electron emitting means may be a linearelectronic accelerator capable of producing a direct current potentialin the range of about 100,000 to about 500,- 000 volts. In such adevice, electrons are ordinarily emitted from a hot filament andaccelerated through a uniform voltage gradient. The electron beam, whichmay be about inch in diameter at this point, may then be scanned to makea fan-shaped beam and then passed through a metal 'Wll'ldOW, e.g., amagnesium-thorium alloy, aluminum, an alloy of aluminum and a minoramount of copper, etc., of about 0.003 inch thickness.

It will be understood by those skilled in the art that modifications canbe made within the foregoing examples without departing from the spiritand scope of the invention as set forth in the following claims.

We claim:

1. A paint polymerizable by ionizing radiation which, exclusive ofnonpolymerizable solvents, pigments and particulate mineral filler,consists essentially of a divinyl compound formed by first reacting onemolar part of a diepoxide with two molar parts of an alpha-betaolefinically unsaturated monocarboxylic acid selected from acrylic acidand methacrylic acid and subsequently reacting the resultant divinylester condensation product with two molar parts of a saturated acylhalide.

2. A paint in accordance with claim 1 wherein said diepoxide has amolecular weight below about 2,000.

3. A paint in accordance with claim 1 wherein said diepoxide has amolecular weight in the range of about 140 and to about 500.

4. A paint in accordance with claim 1 wherein said acyl halide is thechloride of a C C saturated monocarboxylic acid.

5. A paint in accordance with claim 1 wherein said acyl halide is thechloride of a C -C saturated monocarboxylic acid.

6. A paint in accordance with claim 1 wherein said acyl halide is thebromide of a C C saturated monocarboxylic acid.

7. A paint in accordance with claim 1 wherein said acyl halide is thebromide of a C C saturated monocarboxylic acid.

8. A paint in accordance with claim 1 wherein an amount up to but lessthan 50% of said divinyl compound is replaced with a tetravinyl compoundconsisting essentially of carbon, hydrogen and oxygen and having amolecular weight below about 2,350.

9. A paint in accordance with claim 1 wherein an amount up to but lessthan 50% of said divinyl compound is replaced with a tetravinyl compoundconsisting essentially of carbon, hydrogen and oxygen and having amolecular weight in the range of about 220 to about 1100.

10. A paint in accordance with claim 1 wherein an amount up to but lessthan 50% of said divinyl compound is replaced with a tetravinyl compoundconsisting essentially of carbon, hydrogen and oxygen and having amolecular weight in the range of about 220 to about 650.

11. A paint in accordance with claim 1 wherein an amount up to but lessthan 50% of said divinyl compound is replaced with a different divinylcompound consisting essentially of carbon, hydrogen and oxygen andhaving a molecular weight below about 2,600.

12. A paint in accordance with claim 1 wherein an amount up to but lessthan 50% of said divinyl compound is replaced with a different divinylcompound consisting essentially of carbon, hydrogen and oxygen andhaving a molecular weight in the range of about 220 to about 1,100.

13. A paint in accordance with claim 1 wherein an amount up to but lessthan 50% of said divinyl compound is replaced with a different divinylcompound consisting essentially of carbon, hydrogen and oxygen andhaving a molecular Weight in the range of about 220 to about 65 0.

14. A paint polymerizable by ionizing radiation which, exclusive ofnonpolymerizable solvent, pigments and particulate mineral filler,consists essentially of a nonpolymerizable solvent and a divinylcompound formed by first reacting one molar part of a diepoxide with twomolar parts of an alpha-beta olefinically unsaturated monocarboxylicacid selected from acrylic acid and methacrylic acid and subsequentlyreacting the resultant divinyl ester condensation product with two molarparts of a saturated, aliphatic monocarboxylic acid halide.

15. A paint in accordance with claim 14 wherein an amount up to but lessthan 50% of said divinyl compound is replaced with a tetravinyl compoundhaving a molecular weight in the range of about 220 to about 1,100 andformed by first reacting one molar part of the diepoxide with two molarparts of an alpha-beta olefinically unsaturated monocarboxylic acidselected from acrylic acid and methacrylic acid and subsequentlyreacting the resultant ester condensation product with two molar partsof a vinyl unsaturated acyl halide.

16. A paint in accordance with claim 14 wherein an amount up to but lessthan 50% of said divinyl compound is replaced with a tetravinyl compoundhaving a molecular weight in the range of about 220 to about 650 andformed by first reacting one molar part of a diepoxide with two molarparts of an alpha-beta olefinically unsaturated monocarboxylic acidselected from acrylic acid and methacrylic acid and subsequentlyreacting the resultant ester condensation product with two molar partsof a vinyl unsaturated acyl halide.

17. A paint in accordance with claim 14 wherein an amount up to but lessthan 50% of said divinyl compound is replaced with a dilferent divinylcompound having a molecular weight in the range of about 220 to about1100 and formed by first reacting one molar part of a diepoxide with twomolar parts of an alpha-beta olefinically unsaturated monocarboxylicacid selected from acrylic acid and methacrylic acid and subsequentlyreacting the resultant ester condensation product with two molar partsof an alpha-beta olefinically unsaturated acyl halide having an aromaticradical afiixed to the beta carbon of the olefinic linkage.

18. A paint in accordance with claim 14 wherein an amount up to but lessthan 50% of said divinyl compound is replaced with a hydroxylateddivinyl compound having a molecular weight in the range of about 220 toabout 1,100 and formed by reacting one molar part of a diepoxide withtwo molar parts of an alpha-beta olefinically unsaturated monocarboxylicacid selected from acrylic acid and methacrylic acid.

19. A paint in accordance with claim 14 wherein an amount up to but lessthan 50% of said divinyl compound is replaced with the divinyl compoundhaving a molecular weight in the range of about 220 to about 1,100 andformed by first reacting one molar part of a diepoxide with two molarparts of an alpha-beta olefinically unsaturated monocarboxylic acidselected from acrylic acid and methacrylic acid and subsequentlyreacting the resultant condensation product with two molar parts of anaromatic substituted saturated acyl halide.

20. The paint in accordance with claim 14 wherein an amount up to butless than 50% of said divinyl compound is replaced with a differentdivinyl compound having molecular weight in the range of about 220 toabout 1,100 and formed by reacting a monoepoxide with an alpha-betaolefinically unsaturated monocarboxylic acid selected from acrylic acidand methacrylic acid and then reacting the resultant ester condensationproduct with a vinyl unsaturated acyl halide.

21. In a method for painting a substrate wherein a filmforming solutionis applied as a paint fihn to a surface of said substrate andcrosslinked thereon by exposing the coated surface to ionizingradiation, the improvement wherein said film-forming solution, exclusiveof nonpolymerizable solvents, pigments and particulate mineral filler,consists essentially of a divinyl compound formed by first reacting onemolar part of a diepoxide with two molar parts of an alpha-betaolefinically unsaturated monocarboxylic acid selected from acrylic acidand methacrylic acid and subsequently reacting the resultant divinylester condensation product with two molar parts of a saturated acylhalide.

122. An article of manufacture comprising in combination a substrate anda polymerized coating of paint formed upon an external surface thereofby applying to said surface a film of substantially even depth of afilm-forming solution which, exclusive of nonpolymerizable solvents,pigments and particulate mineral filler, consists essentially of adivinyl compound formed by first reacting one molar part of a diepoxidewith two molar parts of an alpha-beta olefinically unsaturatedmonocarboxylic acid selected from acrylic acid and methacrylic acid andsubsequently reacting the resultant divinyl ester UNITED STATES PATENTS3,466,259 9/1969 Jernigan 260836X FOREIGN PATENTS 1,006,587 10/ 1965Great Britain 26 0-486 ALFRED L. LEAVITT, Primary Examiner I. H.NEWSOME, Assistant Examiner US. Cl. X.R.

ll7l38.8, 161; 204-15915, 159.16; 260'410.5, 475. 485, 486, 835, 836,857

